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US9181143B2 - Process for the production of olefins and use thereof - Google Patents

Process for the production of olefins and use thereof Download PDF

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Publication number
US9181143B2
US9181143B2 US14/241,323 US201214241323A US9181143B2 US 9181143 B2 US9181143 B2 US 9181143B2 US 201214241323 A US201214241323 A US 201214241323A US 9181143 B2 US9181143 B2 US 9181143B2
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Prior art keywords
reaction
recited
ionic liquid
light alcohols
olefins
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US14/241,323
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US20150087866A1 (en
Inventor
Roberto Werneck do Carmo
Paulo Luiz De Andrade Coutinho
Luis Fernando Dagnone Cassinelli
Roberto Fernando de Souza
Marcelo Mignoni
Luiza Roza
Edson Comin
Andrieli Dias Martins
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Universidade Federal Do Rio Grande
Braskem SA
Universidade Federal do Rio Grande do Sul UFRGS
Ideom Technologia Ltda
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Universidade Federal Do Rio Grande
Braskem SA
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Priority to US14/241,323 priority Critical patent/US9181143B2/en
Assigned to IDEOM TECNOLOGIA LTDA., UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL reassignment IDEOM TECNOLOGIA LTDA. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COMIN, Edson, DE SOUZA, ROBERTO FERNANDO, Martins, Andrieli Dias, DAGNONE CASSINELLI, LUIS FERNANDO, DE ANDRADE COUTINHO, PAULO LUIZ, MIGNONI, Marcelo, DO CARMO, ROBERTO WERNECK, ROZA, LUIZA
Assigned to BRASKEM S.A. reassignment BRASKEM S.A. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: IDEOM TECNOLOGIA LTDA.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to a process for the production of olefins by dehydrating light alcohols using ionic liquids as an acidic medium. Furthermore, the present invention relates to the use of such olefins, for example in the production of polymers and monomers such as ethylene glycol.
  • Ethylene is one of the main base products used in the petrochemicals industry, and it is used in the synthesis of products of great importance such as polyethylene, ethylene oxide, and many other products, either or not deemed to constitute commodities.
  • ethylene is produced by way of thermal cracking of naphtha. This is a widely used process, both optimized and profitable, which however is hindered by the conceptual question of the use of petroleum in large amounts, being that this raw material is in itself a finite resource.
  • Such processes in industrial use, usually employ acid catalysts such as ⁇ -Al 2 O 3 and zeolite HZSM-5.
  • acid catalysts such as ⁇ -Al 2 O 3 and zeolite HZSM-5.
  • the Al 2 O 3 requires higher reaction temperatures (between 400 and 500° C.), while the use of zeolites of the HZSM-5 type allows the use of lower temperatures.
  • Various other catalysts such as silica-alumina, metal oxide, supported phosphoric acid and phosphate, may be used.
  • the same acidity that facilitates the dehydration reaction leads to the formation of coke deposits and to the corresponding deactivation of the catalysts, thereby entailing an increase in operating costs inherent to the reactivation of these catalysts, or still worse, the substitution thereof.
  • the presence of water in the starting ethanol reduces the deactivation caused by formation of coke, but increases the consumption of power and leads to the dealumination of the zeolites at high temperatures.
  • the technical problem to be solved by the present invention is related to the high temperature that is required in the prior art processes to achieve the conversion of the alcohol to olefin.
  • the ionic liquids based on imidazole are liquid organic compounds that have drawn much attention, both scientifically and technologically, due to their very peculiar properties, such as high stability, low (or null) volatility, different solubility with polar and non-polar compounds, high ionic and electrical conductivity, etc.
  • high acidity evidenced by some of these materials Such is the case in the olefin alkylation reactions.
  • U.S. Pat. No. 7,208,605 relates to the use of an IL [ionic liquid] with an appended acidic group for general or specific acid catalysis, either as a pure material, or as a solution in another ionic liquid or molecular solvent.
  • Such reactions include, but are not limited to, Fischer esterification, pinnacol rearrangement, alcohol dehydration, rearrangements, isomerizations, Friedel-Crafts alkylation and acylation, or aromatic nitration.
  • US2009/0062571 discloses a process for dehydrating alcohols, polyalcohols and alcoholates having at least one CH group in the ⁇ position for the production of alkenes and ethers with ionic liquid.
  • ionic liquids used are the imidazole derivatives.
  • the document teaches a process for the dehydration of alcohols in order to produce alkenes, there are only used higher alcohols in the process.
  • the document does not suggest the use of ionic liquids for the dehydration of light alcohols in order to produce alkenes. It is known that the dehydration of light alcohols is rendered difficult by chemical factors (reactivity and kinetics).
  • the Chinese paper Dehydration of Ethanol Catalyzed by Acidic Ionic Liquid discusses the dehydration of ethanol catalyzed by an acid ionic liquid.
  • the document discloses the use of the ionic liquid 1-(4-sulphonic acid)butyl-3-methylimidazole hydrogen sulfate and sulfuric acid.
  • the document discloses that the dehydration reaction occurs at a temperature that varies between 120 and 220° C., a high temperature that results in a considerable energy spending and impacts in olefin selectivity.
  • US2009/0118558 discloses a process for dehydrating alcohols, for the purpose of producing olefins and/or ethers using an ionic liquid.
  • the dehydration reactions occur at a temperature of 100 to 400° C.
  • the ionic liquid used may be derived from imidazole.
  • the process takes place at high temperatures, resulting in heavy energy costs.
  • the process exhibits low selectivity for ethylene and formation of ether, and the conversion to ethylene mentioned in the examples is up to 12%.
  • One disadvantage of this process is the fact that there is an additional step where the water needs to be condensed out from the olefin and/or ether product.
  • the object of the present invention consists in the provision of a process for the dehydration of light alcohols intended for the production of olefins, with low generation of byproducts and reduced energy consumption, in addition to requiring a simple system for purifying the olefin having been generated, without requiring the addition of acids or other solvents in reaction.
  • the process of dehydration of light alcohols is conducted at low temperature, thereby achieving high selectivity to olefins and requiring a purification process that is simple, due to the low rate of formation of impurities such as CO, H 2 , acetaldehyde and CO 2 .
  • olefins for example, in the production of polymers and other monomers, such as ethylene glycol. It is a further object of the present invention to use such olefins for the production of propylene.
  • FIG. 1 depicts a block diagram of the process for the production of olefins according to the present invention.
  • FIG. 2 depicts the block diagram of the process for the production of olefins, wherein the purification step is comprised of two steps.
  • FIG. 3 depicts gas chromatography analysis-ethylene standard (retention time: 10.5 min.).
  • FIG. 4 depicts gas chromatography analysis-ethylene produced (retention time: 10.4 min.).
  • the present invention relates to a process for the production of olefins from the dehydration of light alcohols using ionic liquids, characterized by occurring at low temperature and comprising the following steps:
  • the light alcohols used in the present invention have 2 to 8 carbon atoms.
  • the light alcohols of the present invention have 2 to 4 carbon atoms, more preferentially from 2 to 3 carbon atoms.
  • the light alcohols used in the present invention may originate from sugarcane, corn, beetroot, and biomass, among others.
  • the ionic liquids used in the present invention are organic compounds of formula R 1 ImR 2 X, wherein R 1 is an alkyl group comprising from 1 to 20 carbon atoms, R 2 is an alkyl group comprising from 1 to 10 carbon atoms, Im is the imidazole ring (C 3 N 2 H 3 ) and X is an anion selected from the group consisting of [HSO 4 ] ⁇ , [SO 4 ] ⁇ 2 , [NO 3 ], [BF 4 ] ⁇ , [(Rf) 2 BF 3 ] ⁇ , [(Rf) 2 BF 2 ] ⁇ , [(Rf) 3 BF] ⁇ , [(Rf) 4 B] ⁇ , [B(CN) 4 ] ⁇ , [PO 4 ] ⁇ 3 , [HPO 4 ] ⁇ 2 , [H 2 PO 4 ] ⁇ , [alkyl-OPO 3 ] ⁇ 2 , [(alkyl-O) 2 PO
  • the anion X of the ionic liquid is devoid of sulfur atoms.
  • the dehydration reaction of light alcohols of the present invention occurs at a temperature of up to 150° C.
  • the reaction occurs at a temperature in the range of 30 to 100° C., more preferably between 60 and 100° C.
  • the dehydration reaction of light alcohols of the present invention occurs at a pressure of 1 to 20 bar (1 MPa to 20 MPa).
  • the independent process used to remove the water from the reaction can be by adsorption, distillation, evaporation or any other process
  • the process for the production of olefins according to the present invention comprises the following steps, without however being restricted thereto:
  • a stream containing the alcohol (or mixture of alcohols) 2 is contacted with an ionic liquid in a reactor A.
  • the ionic liquid may be directly conveyed to the reactor 1 a or may be added to the returning stream of purified ionic liquid 1 b.
  • the process for the production of olefins according to the present invention comprises the following steps, without being restricted thereto:
  • a stream containing alcohol (or a mixture of alcohols) 2 is contacted with an ionic liquid in a reactor A;
  • the ionic liquid may be conveyed directly to the reactor 1 a or may be added to the returning stream of the purified ionic liquid 1 b;
  • the process for the production of olefins according to the present invention comprises the following steps:
  • the reaction of dehydration of alcohols of the present invention may be conducted under heating to compensate the energy withdrawn by the endothermic dehydration reaction.
  • This heating may be provided in several forms, for example, by heating the reactor, by heating the ionic liquid 1 a to a temperature above the temperature of reaction, heating of the ionic liquid stream that passes the water separation step, or a combination of these, without being restricted thereto.
  • the present invention presents the following advantages:
  • the olefins obtained in the present invention may be useful in the industries of polymers, ethylene glycol, monoethylene glycol, among other products. Furthermore, the olefins obtained in the present invention can be used for the production of propylene.
  • the tests were performed under two different temperatures (80 and 100° C.) by stirring under reflux and feeding the ethanol in batch. After the reaction was completed, the distillation of the residual liquid was carried out to quantify the reaction conversion.
  • a distillation system was coupled.
  • the ethanol feed was made in continuous flow and varied from 0.1 to 0.5 g/min.
  • the temperature employed in the system was varied between 120 to 180° C.
  • the reactor was filled with ranching rings, thus replacing the magnetic stirring.
  • the ionic liquid used in the experiments was methyl-butyl-imidazole tetrafluoroborate (BMI.BF4).
  • the reactions of experiments 1-10 were performed according to the initial reaction system at atmospheric pressure by magnetic stirring, under reflux for time 30 minutes with addition of ethanol per batch.
  • the first five experiments (1-5) were performed at a temperature of 80° C. and the remaining experiments (6-10) performed at a temperature of 100° C. After the ethylene gas formation was stopped, distillation of the residual liquid was carried out to quantify the conversion reaction of ethanol.
  • Reactions 11-13 were heated to 120° C. and the reactions 14-16 were heated at 150° C.; the reaction 17 was heated at 180° C.
  • the reactor was heated using a heating mantle collar with internal control temperature using a thermocouple. Addition of ethanol in the reactor was made in continuous flow with the aid of a properly calibrated metering pump at a rate of addition of ethanol (g/min) as described in the table above. After the prescribed reaction time, as shown in the table above, the final weighing of all the reaction system was performed to quantify the conversion of ethanol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US14/241,323 2011-08-30 2012-08-30 Process for the production of olefins and use thereof Active US9181143B2 (en)

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US201161529028P 2011-08-30 2011-08-30
PCT/IB2012/002201 WO2013030677A2 (fr) 2011-08-30 2012-08-30 Procédé de production d'oléfines et utilisation correspondante
US14/241,323 US9181143B2 (en) 2011-08-30 2012-08-30 Process for the production of olefins and use thereof

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WO2019202406A1 (fr) 2018-04-16 2019-10-24 Braskem S.A. Compositions et articles en eva élastomère d'origine biologique et procédés associés
WO2019202405A1 (fr) 2018-04-16 2019-10-24 Braskem, S.A. Compositions d'eva d'origine biologique et articles et procédés associés
WO2020028699A1 (fr) 2018-08-01 2020-02-06 Braskem America, Inc. Compositions thermoplastiques présentant une ténacité améliorée, articles fabriqués à partir de celles-ci et procédés associés
WO2020049366A1 (fr) 2018-09-07 2020-03-12 Braskem S.A. Compositions de polymère à émission de co2 à faible impact et leurs procédés de préparation
WO2020165660A1 (fr) 2019-02-14 2020-08-20 Braskem S.A. Films d'adhésif thermofusible comprenant de l'eva biosourcé, procédés et articles en ces derniers
WO2020183248A1 (fr) 2019-03-14 2020-09-17 Braskem S.A. Revêtement par extrusion de résine à partir d'un réacteur tubulaire
WO2020234656A1 (fr) 2019-05-20 2020-11-26 Braskem S.A. Compositions adhésives thermofusibles comprenant de l'eva biosourcé, procédés et articles associés
WO2021048634A1 (fr) 2019-09-11 2021-03-18 Braskem S.A. Mousse eva très souple et procédés associés
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WO2022029502A1 (fr) 2020-08-06 2022-02-10 Braskem S.A. Cire de polyéthylène écologique pour adhésifs thermofusibles, enduits et cosmétiques
WO2022069949A1 (fr) 2020-10-02 2022-04-07 Braskem S.A. Formulation de mousse à base d'eva ultra-souple et procédés associés
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WO2022112848A1 (fr) 2020-11-27 2022-06-02 Braskem S.A. Compositions polymères biocompatibles à émission de co2 à faible impact, articles pharmaceutiques et leurs méthodes de préparation
WO2023037168A1 (fr) 2021-09-10 2023-03-16 Braskem S.A. Composition à base de polyéthylène et articles à base de polyéthylène à orientation biaxiale
US11905396B2 (en) 2019-09-30 2024-02-20 Enlightened Product Solutions, LLC Renewably-sourced biodegradable polyolefin packaging, utensils, and containers
WO2024086222A1 (fr) 2022-10-18 2024-04-25 Braskem S.A. Film multicouche à barrière élevée et récipient d'emballage fabriqué à partir de celui-ci
WO2024258902A1 (fr) 2023-06-13 2024-12-19 Braskem S.A. Compositions polymères d'eva souple et articles et procédés associés
WO2025132861A1 (fr) 2023-12-21 2025-06-26 ARLANXEO High Performance Elastomers (Changzhou) Co., Ltd. Polymères de polyoléfine à faible teneur en substances volatiles

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WO2019202406A1 (fr) 2018-04-16 2019-10-24 Braskem S.A. Compositions et articles en eva élastomère d'origine biologique et procédés associés
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WO2020028699A1 (fr) 2018-08-01 2020-02-06 Braskem America, Inc. Compositions thermoplastiques présentant une ténacité améliorée, articles fabriqués à partir de celles-ci et procédés associés
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WO2020165660A1 (fr) 2019-02-14 2020-08-20 Braskem S.A. Films d'adhésif thermofusible comprenant de l'eva biosourcé, procédés et articles en ces derniers
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US11746197B2 (en) 2019-10-15 2023-09-05 Braskem S.A. Bio-based EVA compositions and articles and methods thereof
WO2021079197A1 (fr) 2019-10-22 2021-04-29 Braskem, S.A. Structures multicouches, sachets tenant debout et procédés associés
WO2021189119A1 (fr) 2020-03-24 2021-09-30 Braskem S.A. Équipement pour l'évacuation de déchets et procédé de production d'un équipement pour l'évacuation de déchets
WO2022029502A1 (fr) 2020-08-06 2022-02-10 Braskem S.A. Cire de polyéthylène écologique pour adhésifs thermofusibles, enduits et cosmétiques
WO2022069949A1 (fr) 2020-10-02 2022-04-07 Braskem S.A. Formulation de mousse à base d'eva ultra-souple et procédés associés
WO2022074465A1 (fr) 2020-10-07 2022-04-14 Braskem S.A. Compositions à base d'eva pour articles chaussants
WO2022112848A1 (fr) 2020-11-27 2022-06-02 Braskem S.A. Compositions polymères biocompatibles à émission de co2 à faible impact, articles pharmaceutiques et leurs méthodes de préparation
US11702534B2 (en) 2020-11-27 2023-07-18 Braskem S.A. Biocompatible low impact CO2 emission polymer compositions, pharmaceutical articles and methods of preparing same
WO2023037168A1 (fr) 2021-09-10 2023-03-16 Braskem S.A. Composition à base de polyéthylène et articles à base de polyéthylène à orientation biaxiale
WO2024086222A1 (fr) 2022-10-18 2024-04-25 Braskem S.A. Film multicouche à barrière élevée et récipient d'emballage fabriqué à partir de celui-ci
WO2024258902A1 (fr) 2023-06-13 2024-12-19 Braskem S.A. Compositions polymères d'eva souple et articles et procédés associés
WO2025132861A1 (fr) 2023-12-21 2025-06-26 ARLANXEO High Performance Elastomers (Changzhou) Co., Ltd. Polymères de polyoléfine à faible teneur en substances volatiles

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WO2013030677A2 (fr) 2013-03-07
US20150087866A1 (en) 2015-03-26
EP3453695B1 (fr) 2021-03-24
BR112014004930A2 (pt) 2017-04-18
EP2751056B1 (fr) 2018-09-19
WO2013030677A3 (fr) 2013-07-11
EP2751056A4 (fr) 2015-04-08
BR112014004930B1 (pt) 2020-02-18
EP2751056A2 (fr) 2014-07-09

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